合成气直接制烯烃碳化钴基催化剂的载体效应

doi:10.1016/S1872-2067(18)63153-5

催化学报 ›› 2018, Vol. 39 ›› Issue (12): 1869-1880.DOI: 10.1016/S1872-2067(18)63153-5

合成气直接制烯烃碳化钴基催化剂的载体效应

王新星^a,b, 陈文^a, 林铁军^a, 李杰^a, 于飞^a,b, 安芸蕾^a,b, 代元元^a,b, 王慧^a, 钟良枢^a,c, 孙予罕^a,c

a 中国科学院上海高等研究院, 中国科学院低碳转化科学与工程重点实验室, 上海 201203;
b 中国科学院大学, 北京 100049;
c 上海科技大学物质科学与技术学院, 上海 201203

收稿日期:2018-07-02 修回日期:2018-07-31 出版日期:2018-12-18 发布日期:2018-09-26
通讯作者: 钟良枢
基金资助:
国家重点研发计划（2017YFB0602202）；国家自然科学基金（21573271，91545112，21703278）；中国科学院前沿科学重点研究计划（QYZDB-SSW-SLH035）；中国科学院战略性先导科技专项（XDA21020600）；中国科学院上海高等研究院交叉学科青年创新基金（171001）.

Effect of the support on cobalt carbide catalysts for sustainable production of olefins from syngas

Xinxing Wang^a,b, Wen Chen^a, Tiejun Lin^a, Jie Li^a, Fei Yu^a,b, Yunlei An^a,b, Yuanyuan Dai^a,b, Hui Wang^a, Liangshu Zhong^a,c, Yuhan Sun^a,c

a CAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201203, China;
b University of Chinese Academy of Sciences, Beijing 100049, China;
c School of Physical Science and Technology, ShanghaiTech University, Shanghai 201203, China

Received:2018-07-02 Revised:2018-07-31 Online:2018-12-18 Published:2018-09-26
Contact: 10.1016/S1872-2067(18)63153-5
Supported by:
This work was supported by the National Key R&D Program of China (2017YFB0602202), the National Natural Science Foundation of China (21573271, 91545112, and 21703278), the Key Research Program of Frontier Sciences, CAS (QYZDB-SSW-SLH035), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA21020600), and SARI Interdisciplinary Youth Innovation Research Funding (171001).

摘要/Abstract

摘要：

烯烃是重要的化工原料，一般采用石油热裂解和催化裂解制备.随着石油资源的枯竭，以煤、天然气和生物质等含碳资源经合成气制取烯烃的工艺路线备受关注.其中，合成气经由甲醇或二甲醚间接制取烯烃技术（MTO）已实现工业化应用.与之相比，费托合成直接生产烯烃（FTO）工艺具有流程短、投资和运行费用低等优势，具有良好的工业发展前景.最近我们发现，暴露特定晶面的棱柱状碳化钴表现出很好的合成气制烯烃催化性能，但载体对催化剂结构和催化性能的影响尚不清晰.
本文采用浸渍法制备了一系列负载型钴锰催化剂，系统考察了SiO₂，γ-Al₂O₃和碳纳米管（CNT）对催化剂结构及合成气直接制烯烃催化性能的影响.结果表明，SiO₂及γ-Al₂O₃负载的催化剂较强的钴-载体相互作用抑制了钴锰复合氧化物的形成，而相对惰性的CNT载体则有利于钴锰复合氧化物的生成.通过对反应后催化剂的结构表征，发现SiO₂和γ-Al₂O₃负载的催化剂中出现大量球状的碳化钴颗粒，而CNT负载催化剂中的碳化钴则呈现出具有（101）和（020）暴露晶面的纳米棱柱状结构.将所制备的催化剂用于FTO反应，在265℃，5 bar，空速2000 mL h^-1 g_cat^-1和H₂/CO=0.5的反应条件下，CNT负载的催化剂表现出最佳的催化性能，烯烃和含氧化合物的选择性分别为66.7 C%和25.4 C%，甲烷的选择性仅为2.4 C%，总的烯烃/烷烃比达到8.4，同时烃类产物分布极大地偏离传统ASF线性分布.而对于SiO₂和γ-Al₂O₃负载的催化剂，虽然烯烃的选择性也分别达到68.5 C%和64.7 C%，但甲烷的选择性却升至12.0 C%和5.8 C%，总的烯烃/烷烃比仅为3.5和5.1，烃类产物分布基本符合传统的ASF分布.在150 h的催化剂测试中，CNT负载催化剂表现出很好的催化性能稳定性，甲烷的选择性稳定在2.2 C%，C₂-C₄烯烃的选择性约为30 C%，C₂，C₃和C₄烯烃烷烃比分别稳定在15，19和13.
本研究表明，钴-载体相互作用对碳化钴活性相结构及催化性能具有很大影响，惰性的催化剂载体有利于钴锰复合氧化物的生成，进而促进碳化钴纳米棱柱状结构的形成，从而表现出优异的合成气直接制烯烃催化性能.

关键词: 费托合成制烯烃, 碳化钴, 负载型催化剂, 烯烃, 合成气

Abstract:

Co₂C-based catalysts with SiO₂, γ-Al₂O₃, and carbon nanotubes (CNTs) as support materials were prepared and evaluated for the Fischer-Tropsch to olefin (FTO) reaction. The combination of catalytic performance and structure characterization indicates that the cobalt-support interaction has a great influence on the Co₂C morphology and catalytic performance. The CNT support facilitates the formation of a CoMn composite oxide during calcination, and Co₂C nanoprisms were observed in the spent catalysts, resulting in a product distribution that greatly deviates from the classical Anderson-Schulz-Flory (ASF) distribution, where only 2.4 C% methane was generated. The Co₃O₄ phase for SiO₂-and γ-Al₂O₃-supported catalysts was observed in the calcined sample. After reduction, CoO, MnO, and low-valence CoMn composite oxide were generated in the γ-Al₂O₃-supported sample, and both Co₂C nanospheres and nanoprisms were identified in the corresponding spent catalyst. However, only separated phases of CoO and MnO were found in the reduced sample supported by SiO₂, and Co₂C nanospheres were detected in the spent catalyst without the evidence of any Co₂C nanoprisms. The Co₂C nanospheres led to a relatively high methane selectivity of 5.8 C% and 12.0 C% of the γ-Al₂O₃-and SiO₂-supported catalysts, respectively. These results suggest that a relatively weak cobalt-support interaction is necessary for the formation of the CoMn composite oxide during calcination, which benefits the formation of Co₂C nanoprisms with promising catalytic performance for the sustainable production of olefins via syngas.

Key words: Fischer-Tropsch to olefins, Cobalt carbide, Supported catalyst, Olefin, Syngas

王新星, 陈文, 林铁军, 李杰, 于飞, 安芸蕾, 代元元, 王慧, 钟良枢, 孙予罕. 合成气直接制烯烃碳化钴基催化剂的载体效应[J]. 催化学报, 2018, 39(12): 1869-1880.

Xinxing Wang, Wen Chen, Tiejun Lin, Jie Li, Fei Yu, Yunlei An, Yuanyuan Dai, Hui Wang, Liangshu Zhong, Yuhan Sun. Effect of the support on cobalt carbide catalysts for sustainable production of olefins from syngas[J]. Chinese Journal of Catalysis, 2018, 39(12): 1869-1880.

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合成气直接制烯烃碳化钴基催化剂的载体效应

Effect of the support on cobalt carbide catalysts for sustainable production of olefins from syngas

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